CN115305478A - Preparation method of recyclable efficient composite platinum catalyst and application of efficient composite platinum catalyst in electrocatalysis - Google Patents

Preparation method of recyclable efficient composite platinum catalyst and application of efficient composite platinum catalyst in electrocatalysis Download PDF

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CN115305478A
CN115305478A CN202210803712.1A CN202210803712A CN115305478A CN 115305478 A CN115305478 A CN 115305478A CN 202210803712 A CN202210803712 A CN 202210803712A CN 115305478 A CN115305478 A CN 115305478A
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高广刚
尹迪
刘红
范林林
宫孟娣
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Abstract

The invention provides a preparation method of a recyclable high-efficiency composite platinum catalyst, which comprises [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Preparation of (1) and catalyst Pt/Mo 2 C/Mo 2 Preparation of N @ C-N. The platinum base with the nano cubic structure is preparedElectrocatalyst (Pt/Mo) 2 C/Mo 2 N @ C-N), which shows excellent electrocatalytic activity at a current density of 10 mA cm ‑2 When the catalyst is used, the overpotential is only 13 mV, and the electrocatalysis effect is higher than that of a commercial Pt/C catalyst; furthermore, pt/Mo 2 C/Mo 2 The precursor [ Pt ] can be regenerated after the redox reaction of N @ C-N in the mixed solution of acetonitrile/dichloromethane/hydrogen peroxide II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The method is used for preparing the catalyst in the next cycle, and finally realizes the recycling of the platinum element. The performance of the catalyst after circulation is almost unchanged.

Description

Preparation method of recyclable efficient composite platinum catalyst and application of recyclable efficient composite platinum catalyst in electrocatalysis
Technical Field
The invention belongs to the technical field of recyclable platinum catalyst synthesis, and particularly relates to a preparation method of a recyclable high-efficiency composite platinum catalyst and an electrocatalysis application thereof.
Background
Currently, platinum-based materials make them one of the most promising electrocatalysts with their excellent electrocatalytic activity. However, large-scale application of platinum-based materials is limited due to low abundance and high price of platinum element in nature. Therefore, the effective recovery of the platinum-based electrocatalyst is the most effective method for solving the scarce platinum resource, and is also a technical problem to be solved in the field of catalysts.
The platinum catalyst prepared by the prior art is mainly recovered by the following three methods:
(1) A high-temperature melting smelting method; (2) acid dissolution; and (3) an electrochemical recovery method. Although the above-mentioned techniques have proved to be effective in recovering platinum, there are still drawbacks in terms of implementation, such as the high-temperature melting process not only being energy-intensive, but also resulting in the emission of toxic gases (such as hydrogen fluoride) that severely pollute the environment. The acid dissolution technique inevitably uses high-corrosive acids such as hydrochloric acid, sulfuric acid, nitric acid and aqua regia in the operation process, so that the equipment cost is high, and harmful emissions (such as hydrogen chloride steam, chlorine gas, sulfur dioxide, nitric oxide, nitrogen dioxide and the like) are released in the recovery process. Electrochemical recycling methods typically use corrosive or toxic electrolytes, which also lead to hazardous emissions and secondary pollution.
The common platinum catalyst Pt/C in the prior art has the advantages of 20 percent of Pt content, high cost of the catalyst,
the recovery method of Pt/C catalyst is to dissolve the waste Pt/C catalyst in dilute acid solution by electrochemical or high temperature (150 ℃) mode to extract Pt, and then to deposit on carbon material. However, during this cycle, the electrochemical properties of the recovered Pt/C catalyst are greatly reduced by the aggregation of Pt and the weak force between Pt and carbon as the substrate materialMater. Chem. Phys. 2022, 276, 125439]。
In summary, the platinum catalyst prepared by the prior art has high Pt content and high catalyst cost, and when platinum is recovered, the cost is high, the environmental pollution is large, the risk of operators is high, and in addition, the recovered platinum-based material generally has a large particle size (> 50 mm), and the electrochemical property is greatly reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a recyclable high-efficiency composite platinum catalyst and application thereof in electrocatalysis, and the following purposes are realized: the composite platinum catalyst is prepared, the catalytic effect is ensured, the consumption of Pt is reduced, the recovery method is environment-friendly, the recycling times are high, the catalyst prepared from the recovered catalyst precursor is almost unchanged in catalytic performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
a process for preparing the efficient composite Pt catalyst able to be cyclically used includes [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Preparation of (1) and catalyst Pt/Mo 2 C/Mo 2 Preparation of N @ C-N.
The following is a further improvement of the above technical solution:
the [ Pt ] is II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The preparation method comprises the steps of mixing platinum tetraammine chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]Dissolving in water, stirring at room temperature for 24 hr, and filtering to obtainYellow filtrate, standing the filtrate at 4 deg.C for one week to obtain light yellow transparent crystal [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]。
The tetraammineplatinum chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]The mass ratio of (A) to (B) is 10-12; the mass volume ratio of the platinum tetraammine chloride to the water is 0.07-0.08g.
The catalyst Pt/Mo 2 C/Mo 2 The preparation method of N @ C-N comprises mixing graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Adding into isopropanol, and controlling illumination intensity at 145-155mW/cm at room temperature 2 Stirring for 0.9-1.1h at a stirring speed of 470-500r/min, centrifuging the obtained mixture, washing the separated solid powder with methanol for three times, vacuum drying at 55-65 ℃ for 1.8-2.2h, and calcining at 590-610 ℃ for 1.9-2.1h in a CO atmosphere to obtain the catalyst Pt/Mo 2 C/Mo 2 N@C-N。
The graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The mass ratio of (1); the mass-to-volume ratio of the graphite phase carbon nitride to the isopropanol is 1mg.
The mass content of Pt in the catalyst is 1.55-1.6%.
Said (C) 4 H 9 N) 4 [Mo 8 O 26 ]The preparation method comprises the steps of dissolving sodium molybdate dihydrate in water, adding tetrabutylammonium bromide, and stirring at 74-76 ℃ for 9-11 minutes to form white precipitate; filtering under normal pressure, adding the obtained white precipitate directly into acetone at 44-46 deg.C, stirring slowly until the precipitate is dissolved, crystallizing the dissolved solution at 4 deg.C in dark at low temperature for about one week to obtain crystal (C) 4 H 9 N) 4 [Mo 8 O 26 ]。
The mass ratio of the sodium molybdate dihydrate to the water is 1.3-4.5; the mass ratio of the sodium molybdate dihydrate to the tetrabutylammonium bromide is 1.66-0.67; the volume ratio of the water to the acetone is 1; the stirring is carried out at a slow speed, and the stirring speed is 110-130 r/min.
The catalyst prepared by the method is applied to electrocatalysis.
The invention adopts octamolybdate anion ([ Mo ] 8 O 26 ] 4- ) As a novel carrier of platinum, a mild redox reaction is utilized to further realize the simultaneous conversion and recovery of the carrier and the platinum. The invention firstly adopts octamolybdate (molecular formula is (C) 4 H 9 N) 4 [Mo 8 O 26 ]) With platinum-containing compounds [ Pt (NH) 3 ) 4 ]Cl 2 Formation of [ Pt ] by crystallization reactions in solution II (NH 3 ) 4 ] 2 [Mo 8 O 26 ](abbreviated as Mo) 8 Pt) crystalline material. Then reducing the prepared crystal material in carbon monoxide atmosphere to obtain a composite platinum-based catalyst Pt/Mo with a cubic configuration 2 C/Mo 2 N @ C-N, and the morphology and structure analysis show that the nano platinum particles are distributed on the molybdenum carbide and molybdenum nitride substrates and can be used for electrocatalytic hydrogen production reaction. After the reaction is finished, pt/Mo is added 2 C/Mo 2 Dissolving N @ C-N in acetonitrile/dichloromethane/hydrogen peroxide mixed solution, and performing crystallization reaction at normal temperature to obtain the most original crystal material [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Thereby realizing the recycling of the platinum catalyst in a simple, effective and environment-friendly way.
Compared with the prior art, the invention has the following beneficial effects:
the application designs a brand new polyoxometallate Mo 8 Pt is used as an ideal recovery medium for the reproducible and efficient platinum-based electrocatalyst. Mo is mixed 8 Pt is used as a precursor to carry out simple reduction reaction on graphite-phase carbon nitride to prepare the platinum-based electrocatalyst (Pt/Mo) with a nano cubic structure 2 C/Mo 2 N @ C-N), which shows excellent electrocatalytic activity at a current density of 10 mA cm -2 When the catalyst is used, the overpotential is only 13 mV, and the electrocatalytic effect is higher than that of a commercial Pt/C catalyst.
In addition, pt/Mo 2 C/Mo 2 The precursor Mo can be generated again after the oxidation-reduction reaction of N @ C-N in the mixed solution of acetonitrile/dichloromethane/hydrogen peroxide 8 And Pt is used for preparing the catalyst in the next cycle, and finally, the recycling of the platinum element is realized. The performance of the catalyst after circulation is almost kept unchanged, and the current density of the composite catalyst after five times of circulation is 10 mA cm -2 The overpotential is still only 13 mV.
In the catalyst prepared by the method, the mass percentage of Pt is 1.55-1.6%, preferably 1.58%, the Pt content is low, and the production cost is low.
Drawings
FIG. 1 Mo prepared by the invention 8 An infrared spectrum of (1);
FIG. 2 shows Mo prepared by the present invention 8 Crystal pattern of Pt under light microscope;
FIG. 3 Mo prepared by the invention 8 Molecular structure diagram of Pt;
FIG. 4 shows Pt/Mo prepared by the present invention 2 C/Mo 2 XRD pattern for N @ C-N;
FIG. 5 shows Pt/Mo prepared by the present invention 2 C/Mo 2 TEM (a) and HRTEM (b) images of N @ C-N;
FIG. 6 shows Pt/Mo prepared by the present invention 2 C/Mo 2 XPS plots for N @ C-N;
wherein a is an XPS plot of C1 s; b is an XPS map of N1 s, c is an XPS map of Mo 3d, and d is an XPS map of Pt 4 f;
FIG. 7 Pt/Mo prepared according to the invention 2 C/Mo 2 Comparative plot of electrochemical performance for N @ C-N and commercial Pt/C;
FIG. 8 Mo before and after multiple cycles 8 XRD pattern of Pt;
FIG. 9 Pt/Mo before and after multiple cycles 2 C/Mo 2 Electrochemical performance plot of N @ C-N.
Detailed Description
Example 1
1. (C 4 H 9 N) 4 [Mo 8 O 26 ](abbreviated as Mo) 8 ) The preparation and infrared characterization of (1):
Mo 8 preparation of (2) referenceJ. Am. Chem. Soc. 1976, 98, 8291–8293]。
Sodium molybdate dihydrate (5 g,20.7 mmol) was dissolved in 22 mL of water (pH = 4.7) and then 3.34 g (10.4 mmol) of tetrabutylammonium bromide C was added 16 H 36 BrN. After stirring for 10 minutes at 75 ℃, a white precipitate formed; filtering under normal pressure, adding the obtained white precipitate into 50 mL acetone heated to 45 deg.C, stirring slowly (120 r/min) until the precipitate is dissolved, placing the dissolved solution in refrigerator fresh-keeping layer (temperature is adjusted to 4 deg.C), and crystallizing at low temperature in dark place for about one week to obtain crystal Mo 8 . Its infrared spectrum is shown in FIG. 1, in which 500 cm -1 To 1000 cm -1 Characteristic peak at wavelength and Mo reported in literature 8 The characteristic peaks of (a) are consistent.
2. [Pt II (NH 3 ) 4 ] 2 [Mo 8 O 26 ](abbreviated as Mo) 8 Pt) preparation and structural characterization:
1.1 g of tetraammineplatinum chloride and 0.1 g of Mo 8 Dissolved in 15 mL of water. After stirring at room temperature for 24 hours, filtration was carried out to obtain a yellow filtrate. Standing the filtrate in a refrigerator at 4 deg.C for one week to obtain light yellow transparent crystal Mo 8 Pt (see fig. 2). Performing structure test on the light yellow transparent crystal by using an X-ray single crystal diffractometer, and analyzing data to obtain the accurate structure of the crystal, namely the light yellow transparent crystal is prepared byβType [ Mo ] 8 O 26 ] 4- Anion and two [ Pt ] II (NH 3 ) 4 ] 2+ Cation composition, and the club-polyhedron diagram is shown in figure 3.
3. Platinum/molybdenum carbide/molybdenum nitride @ carbon-nitrogen (Pt/Mo) 2 C/Mo 2 Preparation of N @ C-N):
0.1 mg of graphite phase carbon nitride and 0.1 mg of Mo 8 Pt is added into 6 mL of isopropanol, and the illumination intensity is controlled to be 150 mW/cm at room temperature 2 Stirring at 480 r/min for 1h, centrifuging the obtained mixture, washing the separated solid powder with methanol for three times, vacuum drying at 60 ℃ for 2h, and calcining at 600 ℃ for 2h in CO atmosphere to finally obtain the nano composite material Pt/M with a hollow cubic structureo2C/Mo2N @ C-N catalyst. The prepared catalyst was characterized by X-ray powder diffraction (XRD), transmission Electron Microscope (TEM), and photoelectron spectroscopy (XPS). Wherein in XRD pattern, mo appears at 34.2 °, 37.8 °, 39.6 °, 52.7 °, 56.2 °, 60.2 ° and 69.3 ° 2 Characteristic diffraction peaks of C, at 36.8, 44.3 and 60.0, appear corresponding to Mo 2 Diffraction peak of N (see fig. 4); TEM image as in FIG. 5a shows Pt/Mo 2 C/Mo 2 The N @ C-N catalyst is a hollow cubic structure with dimensions of about 600 nm, while FIG. 5b shows the lattice stripes of 2.7A, 2.4A and 2.2A, respectively, at the sample interface as compared to Mo 2 (002) face of C, mo 2 (111) plane of N and Pt 0 The (111) crystal face of (A) is well matched. In addition, to further determine the electrocatalyst Pt/Mo 2 C/Mo 2 The composition of N @ C-N and the valence state of Pt XPS tests were performed on samples as shown in FIG. 6a, pt/Mo 2 C/Mo 2 The high resolution C1 s XPS spectra of N @ C-N can be decomposed into 3 peaks (281.6 eV, 284.5 eV and 285.5 eV) corresponding to Mo-C, C = C and C-N, respectively, indicating that in addition to Mo, the sample is in addition to Mo 2 Besides C, some simple substance C exists. The XPS spectrum of N1 s (FIG. 6 b) shows 3 peaks that can be assigned to pyridine N (398.0 eV), pyrrole N (399.3 eV) and quaternary ammonium N (401.5 eV), respectively, indicating that there is doping of N in the sample, in addition to which the peak at 395.0 eV can be attributed to Mo-N. From FIG. 6c, it can be seen that the 228.5 eV and 231.5 eV peaks of the Mo 3d XPS spectrum can be attributed to Mo 2 Mo-C bonds in C, while the 229.2 eV and 232.6 eV peaks correspond to Mo 2 Mo-N in N. The Pt 4f spectrum consists of peaks at 70.7 eV and 73.9 eV, which can be assigned to metallic Pt 0 Species (fig. 6 d). The three characteristics mutually authenticate the composite electrocatalyst Pt/Mo prepared by the invention 2 C/Mo 2 N @ C-N was successfully prepared.
Pt/Mo prepared by the invention 2 C/Mo 2 The mass percentage of Pt of the N @ C-N material is 1.58 percent through ICP determination.
4. And (3) electrochemical performance testing:
taking 2 mg of prepared Pt/Mo 2 C/Mo 2 Dispersing N @ C-N electrocatalyst in 4 mL isopropanol dispersant, and mixing the liquidAfter the sound is uniform, the mixture is coated on the surface of a glassy carbon electrode, a three-electrode system is adopted, the electro-catalysis hydrogen production (HER) performance of the catalyst is measured through an electrochemical workstation, and the test result is shown in figure 7, wherein the current density is 10 mA cm -2 In time, pt/Mo 2 C/Mo 2 The overpotential of N @ C-N (Pt content of 1.58%) is the smallest, only 13 mV, lower than that of the commercial Pt/C (Pt content of 20%) (38 mV).
5. Pt/Mo 2 C/Mo 2 Mo in N @ C-N material 8 And (3) regeneration and recovery of Pt:
50 mg of Pt/Mo subjected to electrochemical test (after electrocatalytic hydrogen production) 2 C/Mo 2 N @ C-N was dissolved in 3 mL acetonitrile, 1mL dichloromethane and 1mL H 2 O 2 （H 2 O 2 30%) for 2h, filtering, placing the filtrate in a refrigerator at 4 ℃ for standing for one week to obtain light yellow transparent crystal Mo 8 Pt, mo after 1 cycle 8 Pt; recycling Mo by using the method in the step 3 8 Conversion of Pt to Pt/Mo 2 C/Mo 2 N @ C-N, which is the catalyst after 1 cycle, and the electrocatalytic hydrogen production test is carried out according to the method in the step 4. And (5) recycling the regenerated materials by using the method in the step 5, so that the recycled materials can be recycled for multiple times.
The application carries out 5 times of regeneration cycle operation, and Mo after 1 time, 3 times and 5 times of cycle 8 XRD test is carried out on Pt, and the result shows that Mo is contained before and after circulation 8 The crystal phase structure of Pt remains almost unchanged (see fig. 8). Simultaneously carrying out 1, 3 and 5 times of circulation on the Pt/Mo composite catalyst 2 C/Mo 2 Electrocatalytic hydrogen production performance tests were performed with N @ C-N (see FIG. 9). The results show that the catalyst Pt/Mo was composited through five cycles 2 C/Mo 2 The hydrogen production performance of N @ C-N is basically not changed, and the current density is 10 mA cm -2 The overpotential is still only 13 mV.

Claims (7)

1. A preparation method of a recyclable high-efficiency composite platinum catalyst is characterized by comprising the following steps: comprising [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Preparation of (1) and catalyst Pt/Mo 2 C/Mo 2 Preparation of N @ C-N.
2. The preparation method of the recyclable high-efficiency composite platinum catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: said [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The preparation method comprises the steps of mixing platinum tetraammine chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]Dissolving in water, stirring at room temperature for 24 hr, filtering to obtain yellow filtrate, standing at 4 deg.C for one week to obtain light yellow transparent crystal [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]。
3. The preparation method of the recyclable high-efficiency composite platinum catalyst as claimed in claim 2, wherein the preparation method comprises the following steps: the tetraammineplatinum chloride and (C) 4 H 9 N) 4 [Mo 8 O 26 ]The mass ratio of (A) to (B) is 10-12; the mass volume ratio of the platinum tetraammine chloride to the water is 0.07-0.08g.
4. The preparation method of the recyclable high-efficiency composite platinum catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the catalyst Pt/Mo 2 C/Mo 2 The preparation method of N @ C-N comprises mixing graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]Adding into isopropanol, and controlling illumination intensity at 145-155mW/cm at room temperature 2 Stirring for 0.9-1.1h at a stirring speed of 470-500r/min, centrifuging the obtained mixture, washing the separated solid powder with methanol for three times, vacuum drying at 55-65 ℃ for 1.8-2.2h, and calcining at 590-610 ℃ for 1.9-2.1h in a CO atmosphere to obtain the catalyst Pt/Mo 2 C/Mo 2 N@C-N。
5. The preparation method of the recyclable high-efficiency composite platinum catalyst as claimed in claim 4, wherein the preparation method comprises the following steps:
the graphite phase carbon nitride and [ Pt ] II (NH 3 ) 4 ] 2 [Mo 8 O 26 ]The mass ratio of (1); the mass-volume ratio of the graphite-phase carbon nitride to the isopropanol is 1mg.
6. The preparation method of the recyclable high-efficiency composite platinum catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the mass content of Pt in the catalyst is 1.55-1.6%.
7. Use of a catalyst prepared by the process of claim 1 in electrocatalysis.
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